79061-79-3Relevant academic research and scientific papers
New mixed carbonyl-nitro and -nitrito complexes of manganese and rhenium
Sieker, Anke,Blake, Alexander J.,Johnson, Brian F. G.
, p. 1419 - 1428 (2007/10/03)
Treatment of with Me3NO in CH2Cl2 in the presence of gave the anion cis-- which, on further reaction, yielded the new dianionic trimer 2- containing both bridging nitro- and nitrito-groups.Reactions of , cis--, - or 2- with also produce the same final product.The crystal and molecular structure of the + salt has been established by X-ray diffraction analysis.The molecule 2 crystallises in the triclinic space group P1-.Addition of to in CH2Cl2 yielded a series of mixed carbonyl-nitro/nitrito isomers, which have been characterised in solution.The unusual complex salt 3Cl has been characterised in the solid state by single-crystal X-ray diffraction methods.The molecule crystallises in the monoclinic space group P21/a.
Nucleophilic nitrosylations of metal carbonyls using bis(triphenylphosphine)nitrogen(1+) nitrite
Stevens, Robert E.,Gladfelter, Wayne L.
, p. 2034 - 2042 (2008/10/08)
Bis(triphenylphosphine)nitrogen(1+) nitrite (PPN(NO2)) has been found to be very effective for converting metal carbonyls into nitrosyl carbonyl complexes. The reactions are conducted in dipolar aprotic solvents such as tetrahydrofuran (THF) or acetonitrile and characteristically give high yields with no side products. The reaction has been successfully applied to Fe(CO)5, [Mn(CO)6]+, [Mn(CO)5(CH3CN)]+, [Fe(CO)2(PPh3)2(NO)]+, Mn(CO)4(NO), Mn2(CO)10, Co2(CO)8, Fe3(CO)12, Ru3(CO)12, Os3(CO)12, and Ru6C(CO)17 to generate CO2, a two-electron donor ligand (L), and the product, resulting in replacement of CO and L with NO and a negative charge. A kinetic analysis of the reaction of Fe(CO)5 and PPN(NO2) in acetonitrile verifies that the reaction is first order in iron and nitrite with k = 0.111 ± 0.007 M-1 s-1 at 26 ± 1°C. The addition of a 10-fold excess of PPh3 had no effect on the rate of the reaction. The new nitrosylcarbonylmetalate, [Mn(CO)2(NO)2]-, was characterized by a single-crystal X-ray crystallographic study (P21/a space group, Z = 4, a = 21.890 (5) A?, b = 9.194 (3) A?, c = 17.495 (3) A?, β = 96.25 (2)°), which shows that it has a tetrahedral geometry with disordered NO and CO ligands. Characterization of the new clusters [Ru3(CO)10(NO)]- and [Os3(CO)10(NO)]- establishes that the NO is bridging one edge of the metal triangle, while spectroscopic evidence suggests that [Ru6C(CO)15(NO)]- contains a terminal nitrosyl ligand. Nitrogen-15 magnetic resonance spectra of the bridging nitrosyls exhibit a 400 ppm downfield shift relative to the resonance of mononuclear nitrosyl carbonyl compounds. In some cases PPN(NO2) simply substitutes a NO2- for a carbonyl. This occurs with Co(CO)3(NO) to give the new nitro nitrosyl product [Co(NO2)(C-O)2(NO)]-.
